Additives for Surface and Substrate

Additives for Surface and Substrate Page 1 Basics 2 1.1 Surface tension 2 1.2 Measurement of surface tension 3 1.3 Surface defects 4 1.4 Influences on leveling 4 1.5 Physical processes during drying 5 1.6 Prevention of surface defects 6 1.7 Modification of surface properties 6 1.8 Substrate wetting 7 2 Function of additives 8 2.1 Silicone additives 8 2.2 Acrylate additives 8 2.3 Special additives 8 2.4 Nonionic additives 8 3 EDAPLAN LA 411, EDAPLAN LA 413, 9 4 EDAPLAN LA 402, EDAPLAN LA 403 10 5 EDAPLAN LA 451, EDAPLAN LA 452 11 6 METOLAT 285, METOLAT 288, METOLAT 1299 12 7 METOLAT 362, METOLAT 364, METOLAT 365 13 8 METOLAT 367, METOLAT 368, METOLAT 388 14 PCA 2016

1. Basics Substrate wetting Leveling Surface modification Defects in the surface constitution of coatings are caused by differences of the interfacial tension between coating and substrate. These disturbances occur, when the liquid coating (in this case only water based coatings are regarded) is applied on a non-absorbing substrate. In general, a waterborne coating has a higher surface tension than the substrate, on which it is applied. Therefore the liquid tends to withdraw from the substrate instead of spreading on it, which would be necessary to get a homogeneous surface. A change in the surface tension of the coating is necessary to solve this problem. Table 1 gives an overview of surface tensions for common substrates, liquids and surfactants, which are used in the paint, lacquer and adhesive industry. Leveling defects can also be generated by effects, which are not based on differences in interfacial tension. These are rheological effects, application methods and solvent evaporation. In high pseudoplastic systems the fast build-up of structure prevents a uniform extension of the coating due to which bad leveling is obtained. Application by brush or rough atomisation may also generate leveling defects. The evaporation of solvents can cause local surface tension differences, which create craters. Leveling defects based on physical reasons cannot be cleared by leveling agents. 1.1 Interfacial tension Values of surface tension and surface energy for substrates, liquids and surfactants spread over a wide range. All aqueous coatings cause problems on substrates whose surface energy values are below the surface tension values of the coating. Substrate Surface energy [mn/m] Liquids Solvents Surface tension [mn/m] Surfactants Surface tension [mn/m] Glass 37 Mercury 276 NPEO 35 phosphated steel 43-46 Water 72 PVC 39-42 Diethylenglycol 49 Silicon surfactant ~ 30 Aluminium ~ 40 Xylene 32 Polystyrene 36-42 Butylglycolether 30 Polyether-Siloxan- Zinced steel 35 Alkylbenzene 28-30 Copolymer ~ 20 Polyester 43 White Spirit 25-31 Anionic Polyethylene 32-39 Butylglycol 27 Fluorpolymer ~ 17 Polypropylene 28 Butylacetate 25 Untreated Aluminium Butanol 23 33-35 Organosiloxane ~ 22 untreated steel 29 Isopropanol 22 Polytetrafluorethylene 18 n-octane 21 Dimethylsiloxan pure 21 Hexamethyldisiloxane 16 Isopentene 15 Table 1: Surface tensions and energies of substrates, liquids and surfactants PCA 2016 2

By addition of appropriate additives, the surface tension values of the coating can be lowered under the surface energy value of the substrate. Highly efficient are siloxane and fluoro surfactants. On a given surface a coating will spread or withdraw, depending on the surface tension values. If the surface tension of the coating is higher than the surface energy of the substrate, the coating will withdraw on the substrate in order to obtain the lowest possible common surface with the substrate. The angle, which forms the liquid on the substrate is an indication for the ability of the liquid to spread on the substrate, respectively a possibility to determine the dimension for the surface tension relative to a reference. The angle ϑ 2 has values higher than 90. A typical example for high surface tensions is mercury (see liquid 1). Figure 1: Liquids with different surface tensions In the other case the surface tension of the liquid is smaller than that of the substrate and the liquid spreads on the substrate. In this case the angle ϑ 1 takes values ϑ 1 90. Figure 1: Liquids with different surface tension values In other cases (liquid 2 and 3) the surface tension of the liquid is lower than the surface energy of the substrate und the liquid spreads on the substrate. The value of the angle ϑ 1 is 90. In general the contact angle becomes smaller the better the wetting ability of the liquid. This means that the surface tension of the liquid has low values in comparison to the surface energy of the substrate. 1.2 Measurements of the surface tension Surface tensions and energies of liquids and solids can be determined by different methods. The surface energy of solids is determined with the contact angle method for which liquids with known spreading behaviour and surface tensions are taken as reference. For liquids there are two possibilities: either the contact angle method with a known substrate as reference or the ring method. The contact angle method relies on a liquid or a substrate with known surface tension, depending whether the surface tension of a solid or a liquid shall be determined. On the substrate the liquid spreads or withdraws and by means of the resulting contact angle on the substrate, the surface tension can be determined. In the ring method (also known as method by du Noüy) an inert platinum ring is put into the liquid. The ring is torn out of the liquid measuring the resistance. The ring forms a lamella, which bursts, when the surface tension has exceeded the limit. The force, which is necessary to tear out the ring, and the diameter of the ring, can be calculated as surface tension of the liquid. PCA 2016 3

1.3 Surface defects Surface defects can be caused directly by extension (leveling) of the coating or by insufficient wetting of the substrate. In the applied film the following effects can be observed: crater orange peel fish eyes Bénard cells pinholes shrinkage sagging cissing bad recoatability brush drags (application effects), etc. Most of the defects originate in differences in the interfacial tension. These defects can be removed by addition of appropriate additives. Brush drags and sagging however are caused due to the viscosity of the coating and can be eliminated by changing the rheological properties of the coating. 1.4 Influences on leveling The appearance of leveling defects depends not only on the differences in interfacial tension of substrate and coating but also on the following (physical) parameters: viscosity of the film open time film thickness of the coating evaporation of the solvent drying time method of application bad defoaming contaminations on the substrate surface Viscosity can influence leveling significantly. However, viscosity cannot be changed by leveling or surface additives (if these additives have no direct impact on viscosity or the thickener itself). From a rheological point of view leveling takes place in the shear range of 1 s -1. The viscosity value at this point is relevant for the leveling properties. In general, in comparison between a newtonian and a pseudoplastic rheology modifier, leveling is better with a newtonian type, as viscosity is lower in this shear range. Thixotropic coatings shows better leveling, the higher the time period the system needs to return after shearing to its initial state. The film thickness of a coating also influences leveling. In general, leveling is more critical in thin layers of applied films. The thicker the film, the better is leveling at the surface, given that the drying occurs in a homogeneous way. PCA 2016 4

Additives for Surface and Substrate The drying time influences the conditions of the surface due to solvent evaporation. The faster volatile components of the coating evaporate, the higher concentration differences are within the coating and the bigger are turbulences, which cause leveling defects. 1.5 Physical processes during drying Film formation and drying of a coating occurs by evaporation of the volatile, liquid components and the fusion of binder molecules. In emulsion systems the unification of binder particles occurs with a strong volume contraction. In water reducible systems this contraction is quite smaller. The evaporation of liquid parts result in a permanent change in the surface tension of the coating because the combination of these compounds is altered constantly. At the same time viscosity is changed and due to the evaporation at the surface, concentration differences are built up in the film. Figure 2: Bénard cells (formation in the lacquer, from the top) These processes cause currents of solvents from deeper layers to the surface, which results in turbulences in the coating, which on the other hand influence the surface properties. The currents cause, that more light and volatile particles are transported to the surface, whereas heavy particles, due to differences in density and size, sink to the bottom. Regions of sediments are formed in which more light particles are separated from more heavy ones, which can be observed in the formation of regular pattern on the surface: so called Bénard cells (figure 2). At the borders of these cells surface tension is high, whereas in the middle of the area lower surface tensions are present. PCA 2016 5

Figure 3: changes in the color shade due to formation of Bénard cells In addition to inhomogeneous conditions at the surface, flotation effects can occur, if pigments of different colors and different weight are present. A change in the color shade occurs, because the heavy pigments sediment in the drying period due to currents and turbulences. The lighter pigments swim up in the coating or form borders. This separation of pigments leads to the formation of cells in which the color of the border is different from that in the including areas (figure 3). In unpigmented systems or coatings with only one type of pigment, currents are also caused, which leave a structure on the surface. Mainly orange peel is observed as a consequence. Under extreme drying or evaporation conditions the surface of the drying film can even crack. 1.6 Prevention of surface defects Leveling agents are able to cure or to avoid surface defects by influencing the surface tension of the system. Generally, the surface tension of the coating is lowered. This results in a better wetting of the substrate, but leveling and surface agents are also able to keep the tension constant during drying. Due to this, no differences in surface tension by the evaporation of the solvents results. Other types of leveling agents do not influence the surface tension, but just control the evaporation of solvents due to the fact, that they have a controlled incompatibility. These kinds of additives block the coating surface against a too fast evaporation of volatile compounds, but do not change (lower) the surface tension by themselves. Wetting and dispersing agents can prevent surface defects in pigmented systems by avoiding inhomogeneous pigment distribution and stabilise pigments to protect them from flocculation ( EDAPLAN Polymeric Dispersing Agents). Rheological additives can prevent surface defects in that way, that thickeners are chosen, which do not rise viscosity in the region of shear forces, where leveling occurs and where a build up of structure is not allowed ( TAFIGEL PUR Rheology Modifiers for Aqueous Systems). PCA 2016 6

1.7 Surface modification: Smoothness, Scratch resistance, Hydrophobicity Regarding the film of a coating in first glance, the binder is responsible for the properties and is chosen due to the desired properties for the final requirements. Especially hardness is determined by the binder type. Other properties like smoothness, scratch resistance, gloss or hydrophobicity can be influenced by additives. Smoothness of the surface can be influenced by additives improving scratch and scrub resistance. A smooth surface is not harder, but gives less frictional resistance. This leads to a better gliding on the surface and less mechanical injuries (figure 4). Figure 4: Movement of a rough body relative to a surface If a rough structured body is moved over a rough surface, slip resistance has to be overcome. Slip resistance is the force, which is orientated opposite to the movement. The friction force is independent from the contact surface and only dependent on the structure of the surface. A smooth surface, which shows macroscopically no waves or scars, shows in a microscopically scale up a certain roughness or surface structure (lotus effect, nano particles). In order to increase slip of the surface special additives can be used. They form a film on the surface, which let bodies glide on the surface. Especially modified polysiloxanes are used. Polysiloxanes are surface active products, which orientate on the surface of the film. With their hydrophobic ends, they create a layer on the surface of the lacquer, which equals irregularities. Polysiloxanes are active even in very low dosages. At higher rates they have negative influences on adhesion and tend to stabilize foam ( EDAPLAN LA 411, EDAPLAN LA 413). 1.8 Substrate wetting As discussed previously surface tension of an aqueous coating often has to be reduced in order to achieve spreading and a homogeneous surface of the coating. Surface tension liquid < Surface energy substrate = Wetting A good substrate wetting of the coating is needed to get sufficient adhesion of the dry film. Generally, many wetting agents and solvents are able to reduce the surface tension of an aqueous coating under the surface energy value, which is relevant for a certain substrate. With this lower tension, the coating spreads on the substrate. Often the consistency of the substrate is inhomogeneous and results in the formation of craters, which are formed due to local contaminations. Additionally, the evaporation of solvents can cause punctual changes in the surface tension, which results in craters. Other formulation ingredients, like defoamers, which are too incompatible in the medium, can also change the surface tension of the coating punctually and lead to craters in the applied film. The defoamer PCA 2016 7

has to be chosen carefully and to be adapted to the special requirements ( AGITAN - Defoamers). Surfactants based on polysiloxanes, fluoro based surfactants and special wetting agents overcome local differences in surface tension or wet the substrate surface to improve adhesion (METOLAT 285, METOLAT 288, METOLAT 1299). 2. Effect of additives 2.1 Silicone additives (organically modified polysiloxanes) The most commonly used leveling agents are modified organo polysiloxanes. Simple silicone compounds do not reduce surface tension sufficiently, e.g. on low energetic surfaces like plastics. Polyether modified siloxanes of low molecular weight and surfactant structure, however, lead to a strong reduction of surface tension. Smoothness of the surface is improved and scratch and blocking resistance is increased. In higher dosages silicone additives may reduce adhesion and tend to foam. Therefore they should be used in lower concentrations ( EDAPLAN LA 411, EDAPLAN LA 413). 2.2 Acrylic based additives Acrylate additives do not have a pronounced surfactant structure and do not reduce surface tension. Due to controlled incompatibility they migrate to the surface, where they are accumulated. Acrylic leveling agents minimise especially the waves on the surface of the finished coating. They do not prevent formation of craters, because therefore the surface tension has to be lowered. Acrylates do not show negative effects on the adhesion after recoating. In epoxy systems they can show additional deaerating effects. They are used in higher concentrations than polysiloxanes, but too high levels lead to sticky films (EDAPLAN LA 402, EDAPLAN LA 403). 2.3 Special additives Apart from polysiloxanes and acrylates other additives, based on different chemical structures, can be used, e.g. fluoro surfactants or special esters. They can be used to reduce the surface tension and to control the evaporation of volatile coating components due to their migration to the surface ( EDAPLAN LA 451, EDAPLAN LA 452; METOLAT 285, METOLAT 288, METOLAT 1299). 2.4 Nonionic additives Nonionic surfactants have excellent surface active properties. The hydrophilic part consists of strongly polar chemical bonds ( OH = Alcohol; O = Ether, Combination O CH 2 CH 2 OH = Ethoxylates), the hydrophobic part consists of long chain hydrocarbon tails. This group includes polyoxalkylenes, ethoxylated fatty alcoholes or fatty acids ( METOLAT 362, METOLAT 364, METOLAT 365, METOLAT 367, METOLAT 368, METOLAT 388). PCA 2016 8

3 Polysiloxane additives: EDAPLAN LA 411 EDAPLAN LA 413 EDAPLAN LA 411 EDAPLAN LA 413 Composition Non reactive silicone glycol copolymer Polyethermodified polysiloxane Solubility Soluble in acetone, white spirit, alcohol, Dispersible in water Soluble in non polar and polar systems, partly soluble in water Surface tension Pure product 22.6 mn/m 23.3 mn/m in aqueous solution 0.1%: 33.1 mn/m 0.1%: 38.1 mn/m Flash point > 100 C > 65 C Characteristics Improves slip, leveling and gloss Resistant to hydrolysis Deaerating properties Application Waterborne coatings Waterborne resins Powder coatings High Solids Waterborne and solventborne coatings Transparent systems Parquet coatings based on PU- Acrylics Dosage 0.05 to 0.50% 0.10 to 0.50% We believe all information in this literature to be reliable. No warranties, express or implied are made, any implied warranty of fitness for a particular purpose is expressly disclaimed. We recommend that the prospective user determine the suitability of our materials and recommendations before adopting them on a commercial scale. Patents or other legal rights may not be violated under any given circumstances. PCA 2016 9

4 Acrylate additives: EDAPLAN LA 402 EDAPLAN LA 403 EDAPLAN LA 402 EDAPLAN LA 403 Composition Silicone free acrylic polymer, dissolved in butylglycol Silicone free acrylic polymer, in combination with surfactants Solubility in water After neutralisation soluble soluble Surface tension 35.6 mn/m (pure) 40 mn/m (pure) Flash point 50 C > 100 C Neutralisation 100 g EDAPLAN LA 402 need 3.6 to 4.2 g NaOH or 12.5 to 15.0 g NH 4OH (25%) Acid number: approx.55 mg KOH/g Pre-neutralized Characteristics Improves gloss Reduces haze gloss Silicone free Does not influence water sensitivity Prevent surface defects Deaerating properties Improves gloss Reduces haze gloss Silicone free Does not influence water sensitivity Prevent surface defects Deaerating properties Application All aqueous coatings Printing inks Overprint varnishes All aqueous coatings Printing inks Overprint varnishes Chemical curing systems and 2K reaction systems Dosage 0.50 to 3.0% 0.50 to 3.0% We believe all information in this literature to be reliable. No warranties, express or implied are made, any implied warranty of fitness for a particular purpose is expressly disclaimed. We recommend that the prospective user determine the suitability of our materials and recommendations before adopting them on a commercial scale. Patents or other legal rights may not be violated under any given circumstances. PCA 2016 10

4 Special additives: EDAPLAN LA 451 EDAPLAN LA 452 EDAPLAN LA 451 EDAPLAN LA 452 Composition Anionic ester in ethanol and water Anionic ester and surfactants in water Solubility in water emulsifiable emulsifiable Surface tension 35 mn/m (1% in water) 27 mn/m (1% in water) Flash point 27 C > 100 C Characteristics Improves gloss Reduces haze gloss Silicone free Good recoatability Prevention of surface defects No foam tendency Application Architectural coatings Wood and parquet coatings Automotive OEM and repair Industrial coatings Printing inks and overprint varnishes Dosage 0.10 to 1.0% We believe all information in this literature to be reliable. No warranties, express or implied are made, any implied warranty of fitness for a particular purpose is expressly disclaimed. We recommend that the prospective user determine the suitability of our materials and recommendations before adopting them on a commercial scale. Patents or other legal rights may not be violated under any given circumstances. PCA 2016 11

6 Special anionic ester: METOLAT 285 METOLAT 288 METOLAT 1299 METOLAT 285 METOLAT 288 METOLAT 1299 Composition Anionic ester Anionic ester Anionic ester Solubility in water soluble easy emulsifiable emulsifiable Surface tension 28 mn/m 30 mn/m 28 mn/m Characteristics Wetting agent with low foam tendency Silcone free Recoatable Prevent leveling defects caused by overdosage of defoamers Improves substrate wetting Improves substrate wetting, especially PE, PP and coated aluminium sheets Silcone free Recoatable Improves gloss and color strength in overprint varnishes Improves gloss Prevents orange peel Application Improves incorporation of defoamers, which are difficult to emulsify Defoaming of quaternary ammonium compounds Printing inks Overprint varnishes Packaging coatings Wood coatings Adhesives Dosage 0.10 to 0.50% 0.10 to 2.0% We believe all information in this literature to be reliable. No warranties, express or implied are made, any implied warranty of fitness for a particular purpose is expressly disclaimed. We recommend that the prospective user determine the suitability of our materials and recommendations before adopting them on a commercial scale. Patents or other legal rights may not be violated under any given circumstances. PCA 2016 12

8 Nonionic substrate additives: METOLAT 362 METOLAT 364 METOLAT 365 METOLAT 362 METOLAT 364 METOLAT 365 Composition Combination of nonionic, Blend of nonionic Combination of nonionic, surface active compounds surfactants surface active compounds Solubility in water soluble miscible emulsifiable Surface tension 31 mn/m (1% in water) 26 mn/m (1% in water) 24 mn/m (1% in water) Characteristics Silicone free Recoatable High reduction of surface tension No foam tendency Applications Printing inks Overprint varnishes Dispersion paints Industrial coatings Wood and parquet coatings Adhesives Dosage 0.10 to 2.0% We believe all information in this literature to be reliable. No warranties, express or implied are made, any implied warranty of fitness for a particular purpose is expressly disclaimed. We recommend that the prospective user determine the suitability of our materials and recommendations before adopting them on a commercial scale. Patents or other legal rights may not be violated under any given circumstances. PCA 2016 13

8 Nonionic food contact additives: METOLAT 367 METOLAT 368 METOLAT 388 METOLAT 367 METOLAT 368 METOLAT 388 Composition Polyglycol ester Fatty acid ester Polyglycol ester Solubility in water soluble easy emulsifiable emulsifiable Surface tension 29 mn/m (0.5% in water) 28 mn/m (0.5% in water) 33 mn/m (1.0% in water) Characteristics Improves leveling and substrate wetting Reduces substrate defects Silicone free Recoatable Improves acceptance of pigment pastes Improves defoamer compatibility Defoaming properties Biodegradable product Application Food contact applications Printing inks and overprint varnishes Adhesives Paints and Coatings Food contact applications Compatibility agent Wetting of pigments and fillers Dosage 0.10 to 0.50% 0.10 to 3.0% We believe all information in this literature to be reliable. No warranties, express or implied are made, any implied warranty of fitness for a particular purpose is expressly disclaimed. We recommend that the prospective user determine the suitability of our materials and recommendations before adopting them on a commercial scale. Patents or other legal rights may not be violated under any given circumstances. PCA 2016 14